Basic dyes



Patented June 2, 1970 3,515,733 BASIC DYES Roland Entschel and Curt Mueller, Base], and Walter Wehrli, Riehen, Switzerland, assignors t Sandoz Ltd. (also known as Sandoz A.G.), Basel, Switzerland No Drawing. Continuation of application Ser. No.

356,065, Mar. 31, 1964, which is a continuation-inpart of applications Ser. No. 188,837 and Ser. No. 188,889, Apr. 19, 1962; Ser. No. 250,787, Ser. No. 250,788, and Ser. No. 250,789, Jan. 11, 1963; and Ser. No. 296,362, July 19, 1963. This application Apr. 27, 1966, Ser. No. 545,776 Claims priority, application Switzerland, Apr. 21, 1961, 4,709/61; Jan. 12, 1962, 359/62; Apr. 24, 1962, 4,898/62; Mar. 14, 1963, 3,225/63; May 3, 1963, 5,588/63; Feb. 25, 1964, 2,264/ 64 Int. Cl. C09b 1/16, 1/32 U.S. Cl. 260-377 7 Claims ABSTRACT OF THE DISCLOSURE The invention provides basic dyes of the anthraquinone series corresponding to the formula A represents the radical of a dye of the anthraquinone series free from carboxylic and sulfonic acid groups,

y a substituted or unsubstituted methylene group or an organic divalent radical bound to the adjacent N through such a methylene group,

R a substituted or unsubstituted alkyl, cycloalkyl or aralkyl radical or together with R and the adjacent N atom, a heterocyclic ring system or, together with the bridge member y and the adjacent N atom, a heterocyclic ring system,

R a substituted or unsubstituted alkyl radical or a substituted or unsubstituted cycloalkyl or aralkyl radical or, together with R and the adjacent N atom, a heterocyclic ring system,

R hydrogen or a substituted or unsubstituted alkyl or phenyl radical,

R hydrogen or a substituted or unsubstituted alkyl radical,

n the integer 1 or 2,

m the integer 1 or 2, when n is 2, and

X an anion equivalent to a dye cation.

'wherein The present application is a continuation of eopending application, Ser. No. 356,065, filed Mar. 31, 1964, now abandoned, which is a continuation-in-part of copending applications Ser. No. 188,837, filed Apr. 19, 1962 (now U.S. Pat. No. 3,252,967); Ser. No. 188,889, filed Apr. 19, 1962 (now U.S. Pat. No. 3,252,965); Ser. No. 250,787, filed Jan. 11, 1963 (now abandoned); Ser. No. 250,788, filed Ian. 11, 1963 (now abandoned); Ser. No. 250,789, filed Jan. 11, 1963 (now abandoned); and Ser. No. 296,362, filed July 1-9, 1963 (now abandoned), and relates to new basic dyestuffs.

This invention relates to basic dyes of the anthraquinone series and a process for their production corresponding to the formula wherein A represents the radical of a dye of the anthraquinone series free from carboxylic and sulfonic acid groups,

y a substituted or unsubstituted methylene group or an organic divalent radical bound to the adjacent N through such a methylene group,

R a substituted or unsubstituted alkyl, cycloalkyl or aralkyl radical or together with R and the adjacent N atom, a heterocyclic ring system or, together with the bridge member and the adjacent N atom, a heterocyclic ring system,

R a substituted or unsubstituted alkyl radical or a substituted or unsubstituted cycloalkyl or aralkyl radical or, together with R and the adjacent N atom, a heterocyclic ring system,

R hydrogen or a substituted or unsubstituted alkyl or phenyl radical,

R hydrogen or a substituted or unsubstituted alkyl radical,

n the integer 1 or 2,

m the integer 1 or 2, when n is 1, or 2 when n is 2, and

X an anion equivalent to a dye cation.

The process of the invention is characterized by rewherein A has the meaning cited above and Z represents a substituent which can be replaced by, or

converted into, a group of Formula III.

A preferred mode of operation of the present process for the production of new basic dyes of the anthraquinone series consists in reacting 1 mol of a compound of the formula Aty-EL, (IV) wherein E represents the acid radical of an ester, with n mols of a compound of the formula Another mode of operation of the process consists in reacting 1 mol of a compound of the formula with n mols of a compound of the formula R NHHNR (VI) and quartenizing the reaction product.

A third route leading to the new basic dyes of the anthraquinone series of Formula I is as follows: 1 mol of a compound of formula A- y-E \a lkylene-E 11 (VII) wherein alkylene may be branched or unbranched and contains 1 to 3 carbon atoms, is reacted with 1 mol of a compound of the formula R NHNHR (VIII) A further preferred mode of operation of the process for the production of the new basic dyes of the anthraquinone series is characterized by reacting 1 mol of an amine of the formula with n mols of a halogen amine; or by reacting 1 mol of a compound of the formula with n mols of a halogen amine and quaternizing the reaction product; or by reacting 1 mol of a compound of the formula e.g. methane-, ethaneor butanesulfonic acids, the esters 3 of benzene-sulfonic acids which may be further substituted, such as methyl, ethyl, propyl and n-butyl esters of benzenesulfonic, 2- or 4-methylbenzenesulfonic acid, 4-chlorobenzenesulfonic acid or 3- or 4-nitrobenzenesulfonio acid, methyl chloride, methylbromide and methyl iodide or dimethylsulfate, methyl esters of low molecular alkanesulfonic acid or of benzene-benzenesulfonic acids.

Alkylation or quaternization is carried out preferably in an inert solvent, or in aqueous suspension, or without solvent in an excess of the alkylating agent and at increased temperatures with the addition of a buffering agent if necessary.

The anion or anions X may be organic or inorganic ions, e.g. the ions of methyl sulfate, sulfate, disulfate, perchlorate, chloride, bromide, iodide, phosphorous molybdate, phosphorus tungsten molybdate, benzene sulfonate, 4-chlorobenzene sulfonate, oxalate or maleinate.

Highly suitable as bridge member y are a substituted or unsubstituted methylene group or a divalent or trivalent radical bound to the adjacent N through this group, e.g. (CH where p is the number 1 to 6,

v CH2 C 02 Together with R and the adjacent N atom, y can form a heterocyclic ring system which gives rise to ring groupings such as:

CHr-CH:

These compounds can be obtained, for example, by

reacting a compound of Formulae VII, e.g. dihalogen compounds, with a compound of Formula VIII, e.g.

Ring groupings of this type can be combined torA through a member V; they then correspond to a ,groupi ing of the formula wherein X represents N or CH and the ring may contain other hetero atoms when X stands for CH, and Vmay represent a part of the bridge member y.

The symbols R R R R y, n, m and X may have the same meanings in the anthraquinone pyridine and pyridone series.

ene irnine grouping etc.

Examples of suitable acid radicals E are those of sulfuricv acid, (E=SO H), a sulfonic acid (E=SO R,where Ris a substituted or unsubstituted hydrocarbon radical), and by drogen sulfide (E=SH), but preferably the radicals of the halogen hydracids (E:C1, Br etc.) are employed,

(XII) The reaction of a compound of Formula IV with a hydrazine of the Formula V or VI, or a compound of Formula VII with a hydrazine of Formula VIII is effected preferably in an organic solvent and at temperatures of 50 C. to +250 C. The reaction can also be carried out in aqueous medium, if necessary with the addition of an organic solvent, or without solvent at the above-stated temperatures.

The reaction of an amine of Formulae IX, X or XI with a halogenamine is carried out preferably in an organic solvent and at temperatures of -50 C. to +80" C. The reaction can also be effected in aqueous medium, if necessary with the addition of an organic solvent, at the abovestated temperatures.

The halogenamine can be employed either in gaseous form or in solution in an organic solvent, in water, or in a solvent-water mixture.

The dyes formed are separated by one of the basic operations such as filtration, evaporation and filtration, precipitation from a suitable medium and filtration.

The new dyes are excellent for dyeing, padding and printing materials of polymers containing more than 80 acrylonitrile, e.g. polyacrylonitrile, e.g. Orlon (registered trade mark), and copolymers containing 80-90% acrylonitrile and 10% vinyl acetate, methyl acrylate or methyl methacrylate.

These products are marketed under the following names, most of which are registered trademarks: Acrilan (the copoylmer of 85% acrylonitrile and 15% vinyl acetate or vinyl pyridine), Orlon, Dralon, Courtelle, Crylor, Dynel, etc.

The dyeings on these materials obtained with the dyes of the process possess good fastness to light, washing, perspiration, sublimation, pleating, decatizing, pressing, water, sea water, bleaching, dry cleaning, cross dyeing, and solvents. The dyes have very good solubility in water.

The dyes of the present process are dyed to best advantage from aqueous medium, and it is preferable for the medium to be neutral or acid and of boiling temperature.

The commercially available retarding agents can be used in dyeing without adverse effect, though the new dyes produce perfectly level dyeings on the above-named polymers and copolymers without the addition of these agents. The dyes can be applied in closed equipment and under pressure, as they are highly stable to prolonged boiling. They also give very good dyeings on blend fabrics containing a polyacrylonitrile fiber or acrylonitrile copolymer fiber as one of the components. A selected number of the new dyes are suitable for dyeing polyacrylonitrile in the mass in shades fast to light and wet treatments. The dyes of the present process which pose good solubility 'in organic solvents are suitable for the coloration of oils, paint and lacquer media, and plastics, and for the dyeing of fiberforming materials in the spinning solution. They have many other uses, for example, the dyeing of tannin-treated cotton, wool, silk, regenerated cellulose, synthetic polyamide fibers, and paper, at all stages of manufacture. It has been found that mixtures of two or more dyes of Formula I can be used with good success.

The new dyes are well suited for combination, so that dye salts of the same or different dye classes can be used for producing widely different shades.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 4.46 parts of 1,4-di-(2,6-dimethyl)-phenylaminoanthraquinone are added to 45 parts of sulfuric acid monohydrate at 10-15 and the mixture stirred until everything has dissolved. 3 parts of dichlorodimethyl ether are added in the temperature range of 10-15. On completion of reaction, the reaction product is discharged onto 400 parts of ice, the precipitated compound filtered olf and subsequently rinsed in cold water.

5.43 parts of l,4-di-(2',6'-dimethyl-3'-dichloromethyl)- phenylaminoanthraquinone are added to a mixture of tertiary butyl alcohol and ethanol at 2030. The mixture is heated to and at this temperature 1 part of asymmetric dimethyl hydrazine, dissolved in 10 parts of ethanol, is added dropwise in the course of 1 hour. On completion of reaction the solvent is distilled oil with vacuum, and the dry residue recrystallized from water/ethanol. A good yield is obtained of the blue dye of the formula NHz G369 Further valuable dyes of the authraquinone series which can be produced in accordance with the particulars of Examples 1, 136 and 137 are set out in Table 1 below. They correspond to the formula I R5 1% R4 (XII) Where the symbols R R R R R R R and R have the meanings assigned them in the said table.

The anion X may be any one of those named in the specification. In the following Tables 1, 2, 3 and 4 the symbols K K K (2 K K K and K represents the followmg groupings:

NH2 6-) K1 the grouping 1 I(C 3)2] NH2 69 K2 the grouping I I(CzH5)2:lX

NHz G K; the grouping I I(CzH4OH)2]X 0112-0112 ea K the grovping N X CH2OH2 NHz OHz-CHz s;

CH2 x CHz-C 2 NHz CHz-CHz G9 o X CHz-Oz CH=N 9 CH=N NHz

The symbols K K K K K K and K in the individually presented dyestuffs are chosen from the series K5 the grouping N K6 the grouping N K the grouping N displayed above. These groupings can be exchanged in M mo o o mz mo me Q v o 52 M m m m ,sfiorw O NZ m 05% m 08am m m m m QMINEHO 3225mm 52 m o m2 m m m m S 0 M EO m 3 m m 3 m MMLHHO I l 520K MMHDIHHZ m G mo m Hm Hm m n: M mo A v o 6% m we m m m m a 6Q m0 mm Z m m m m w -MTLHHO my 5Q m0 Hm m2 m m m m 1. M SMO :5 mo m 52 m M m m @MHLHHO an mo m wMLmo m2 m m m m w G en mo m .MLwS 52 m m m m 3 7 Q am mo m nMLmo Ez m m m m ANY 6 325 mo m 52 m m m m 1 M MO 02 295mm O0 in mm m 5H 3H m 5H 5H 5 253 fiomqo mfiwhv m5 2 mm M W O O O mz m O sash/3m O 52 m m m m $25 Hz 0 mz m m m m A MT mO .Em mo O @1 E2 m m m m MH mO NZ m2 m m m m o 0 m z mO m Z HHO M wv oo mum nn oo m0 "m0 68535 No m 52 M m m N mz mo -MH mnw OO m0 WZ HHO HHZ 3 &2m m O NZ m M H m 3 M mO OO .50; 52 m mo o Ez m m m m HmHZ HHO -M mnw OO 6mm mo m M o mz m m m m umnz mo 0a m m m m mz mO MH NO OO HHZ NO 52$ 52 m o mz m m m w "dz oinawfl AU .m 3m 5 3 5 5 233253 :22" do M598 an s 2 an m m fiz m m m m M amo Q mo an mv m m .mhz m m m m 32m AHV m m mofi o mz m m m m M mo .520 .moglmz m m Omz m m m m M mo an A L V M m mo mz m m N N M fio 6Q QMHOIAUYEHZ mm m mo mz m m m m mo M Mo 'AU m m mo mz m m M M me an AM v m m Eo mz w m m m M mo an AU m m mo mz m m m m Q mo an mv m m #6 54 m m m m M mo 32m Al v m m mo mz m m m m GHLNO 02 035mm 8 .m .m E i m m 8 m 0 ODQQ ma e mflohw on 88 5 6Q m Hm mz m m m m 0% 6:3 swag-mu HH "0 m m m m ogan-NZ ...iww m N Q m m m m 2 m M EO HHZ M N H m .5 m m 52 m m m m 6Q Hm m mz Hm Hm m m 5 fi mo oo mz mo m m 52 m m m m Q fi m m "mo 52 m m m m JG QHO .055 flmmwuom o o mz mu Hm NHHZ m m m m MH|N..EHO| O O HHZ HHO HMO mm 585 ELMOIMQMOLMOIMZIOIMZ m m O NZ m m m m 8 8D MO HONO WO MZ O MZ m m E Z M m m m 6G W O H-Z m #0 m m m m m 62m O m M o o EZ m m m m mm .5 0 m m EQ OLEA mo m m we L Mm- NG an EOIOmZ m m mo O mz mo m m m hw QHLHO QH WO 438w HQIOIMZ m m mo o mz m 6 6 m w 2w -M HHO L .QEQ mmflwbom FMLHHO|OIMHZ m m HH O m m m m mm "who 7 1 .386 QLMQIOIMZ m m O mz m m m m xw mo .35 QLMOIOLMZ m m 52 m m m m "MO 02 QEEQ CV SH m Sm JH m m mm m 33253 53 no N538 23 w w nm Q 3 33 3 3 3 3 6Q .MlHnOIOOl-MZIOlHmZ m m NZ Hm m m m 3 3 3 3 3 3 swim imlomnollo mZ O mZ m um mm? m m m m l I no 3 3 33 3 3 3 3 22E 33 fi fio oo mz fio o mz m m mo m m m m 5 "m0 nmmu 62m W H M O NZ m N E m M M m mo Ammo 3 3 033 3 3 3 3 Q fi fi M E0 E2 m m m m M mO O O|HHZLMHW 6Q "moo! m2 m m mo mz m m w m MH WO O o mz mnw 6Q .MOO HZ m m fimz m m m m M HFO'O O mZ mO Q HMO .mooIOmZ m H E2 m m m w AND 2m fi flo oo mz mo o wz m m m m m m "62 BQEE Qv m M Sm 3m 3m 3m 5 m 35532323 :33 o 5 b sm 6Q QIEGIMZIOUIOEZ M m 52 m m M m 8H E MZ OO O MZ m M 2 E m m m n: 3.836 0 m m O mz m m m m w: MTIQHOIO O mz 8Q 0 m E0 52 m m m m E M mo o o mz 3n O MZ m m mo mz m m m m w: QHILNOIOOIHHZH 32m O m m 52 m w m m m: GH mmHO O O mz an O m M Ne w m m m w: MT mO -O OIIHHZ 0 m m mo m m m m m: -M|HGOIO OIHHZ 6Q O m N No N m m m N: M fimo o o mz 520T? -M|JHO|O OIWZ|O|WZ m Hm m0 Hm m m m 1.3M :55 QIEOIOUIMZIOIHHZ m m mofi o mz m m m m 5: .836 filfioloolmzlolmz m m @mz m m m m 5 "dz QEEEW Qv SH "m SH SH a p m 333253 23 no M QEV 2 8 82m The following are shown as eiramples from the anthraquinone pyridine and pyridone series:

EXAMPLE 166 EXAMPLE 167 I NHGNE-COr-GHFE EXAMPLE 169 CH orange EXAMPLE 170 34 EXAMPLE 171 4.46 parts of 1,4-di-(2'-,6'-dimethyl)-phenylaminoanthraquinone are added to 45 parts of sulfuric acid monohydrate. at 1 015 and the mixture stirred until everything all has dissolved. 3 parts of dichlorodimethyl ethe rare added in the temperature range of 10-15. On completion of reaction, the reaction product is discharged onto 400 parts of ice, the precipitated compound filtered oil and subsequently rinsed in cold Water.

5.43 parts of 1,4-di-(2 ,6'-dimethyl-3'-dichlor0methyl)- phenylaminoanthraquinone are added to a mixture of tertiary butyl alcohol and ethanol at -30". The mixture is heated to 80 and at this temperature 1.5 parts of asymmetric diethyl hydrazine, is dissolved in 10 parts of ethanol, are added dropwise in the course of 1 hour. On completion of reaction the solvent is distilled off with 1 vacuum, and the dry residue recrystallized from water/ ethanol. A good yield is obtained of the, blue dye of the formula CH CHz-Ka 59$ CH3 f 2 2 NH EXAMPLE 172 3.16 parts of l-methylamino-4-bromoanthraquinone are stirred into parts of iso-amyl alcohol, 1.3 parts of anhydrous potassium acetate, 1 part of cuprous chloride, 1 part of copper benzene and 1 part of chlorethyl amine are added and the mass heated at 100430. It is stirred at this temperature until condensation is complete. and then unloaded onto 400 parts of ice. The precipitate is filtered 01f, washed with Water until neutral, and then entered into 50 0 parts of dioxane, heated at 60 and filtered free from undissolved constituents. The filtrate is then run onto ice and the pure l-methylamino-4-chloroethylaminoanthraquinone filtered off.

The condensation reaction with the asymmetrical diethyl hydrazine proceeds similarly to the reaction described in the preceding example. The blue dye obtained has the formula NH-CH3 The identical dye is arrived at by starting from l-methylamino-4-hydroxyanthraquinone in the. leuco form, condensing with chlorethyl amine with the addition of boric acid, and quaternizing with diethyl hydrazine in the above-described manner.

NO NZ M JHO HO OO NZ MU 3H0 -NO NZ AMO NO O O HZ NU HMO M WD OO NZ NO m0 M m NO NZ mfi 6Q .H m M JH E m O 52 1 o 2mm .5 6 m m mO AHV NZ O 52 M mo mc w o .920? "O a m m QHOGNZ m WOO mz 3 M mo an 6 n m m w mo momo mo mz m m l is 62m 6 n m m mz wo mhm m m mo mz a:

QwO JH mHO O O u m 0 02 oEBmnH a E N d M Sm i. a SH on a bom 23 no M PQ 25 E u nm 

